Skip to main content
SpringerLink
Log in

Enantioselective extraction of clorprenaline enantiomers with hydrophilic selector of sulfobutylether-β-cyclodextrin by experiment and modeling

  • Published:
Journal of Central South University Aims and scope Submit manuscript

Abstract

Enantioselective extraction of hydrophobic clorprenaline (CPE) enantiomers from organic phase to aqueous phases with sulfobutylether-β-cyclodextrin (SBE-β-CD) as the selector was investigated with insight into a number of important process variables, such as the type of organic solvent, concentration of selector, pH, and temperature. Equilibrium of the extraction system was modeled using a reactive extraction model with a homogeneous aqueous phase reaction. The important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic CPE were determined as 0.3 and 8.93, respectively. The equilibrium constants of the complexation reaction with SBE-β-CD were determined as 152 and 110 L/mol for R- and S-CPE, respectively. Results show that the experimental data agree with the model predictions perfectly. Comprehensively considering the experiment and model, the extraction conditions are optimized and the best extraction conditions are: pH of 6.0, SBE-β-CD concentration of 0.04 mol/L, and temperature of 5 °C, providing the enantioselectivity (α) of 1.25, the fraction of R-CPE (φ R) in aqueous phase of 0.71 and performance factor (p f) of 0.025.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. ANDREW J H, KWANT G J, de VRIES G J. Continuous separation of racemic 3,5-dinitrobenzoyl-amino acids in a centrifugal contact separator with the aid of cinchona-based chiral host compounds [J]. Chemistry A European Journal, 2009, 15 (9): 2111–2120.

    Article  Google Scholar 

  2. BREUER M, DITRICH K, HABICHER T, HAUER B, KEΒELER M, STURMER M, ZELINSKI T. Industrial methods for the production of optically active intermediates [J]. Angewandte Chemie International Edition, 2004, 43: 788–827.

    Article  Google Scholar 

  3. LORENZ H, PERLBERGA, SAPOUNDJIEV D, MARTIN P E, SEIDE-MORGENSTERN A. Crystallization of enantiomers [J]. Chemical Engineering and Processing, 2006, 45: 863–873.

    Article  Google Scholar 

  4. JU Xin, PAN Jiang, YU Hui-lei, LI Chun-xin, XU Jian-he. Improving pseudomonas sp. esterase performance by engineering approaches for kinetic resolution of 2-acetoxyphenylacetic acids [J]. Biochemical Engineering Journal, 2011, 57: 63–68.

    Article  Google Scholar 

  5. KLERCK K D, MANGELINGS D, HEYDEN Y V. Supercritical fluid chromatography for the enantioseparation of pharmaceuticals [J]. Journal of Pharmaceutical and Biomedical Analysis, 2012, 8475: 1–16.

    Google Scholar 

  6. ATES H, MANGELINGS D, HEYDEN Y V. Chiral separations in polar organic solvent chromatography: Updating a screening strategy with new chlorine-containing polysaccharide-based selectors [J]. Journal of Chromatography B, 2008, 15857: 1–8.

    Google Scholar 

  7. SCRIBA G K E, Fundamental aspects of chiral electromigration techniques and application in pharmaceutical and biomedical analysis [J]. Journal of Pharmaceutical and Biomedical Analysis, 2011, 55: 688–701.

    Article  Google Scholar 

  8. REIJENGA J C, INGELSE B A, EVERAERTS F M. Training software for chiral separations in capillary electrophoresis [J]. Journal of Chromatography A, 1997, 72: 195–202.

    Article  Google Scholar 

  9. WANG Zhao, CAI Chang-qun, LIN Yong-tao, BIAN Yong-ru, GUO Hong-qin, CHEN Xiao-ming. Enantioselective separation of ketoconazole enantiomers by membrane extraction [J]. Separation and Purification Technology, 2011, 79: 63–71.

    Article  Google Scholar 

  10. STEENSMA M, KUIPERS N J M, de HAAN A B, KWANT G. Analysis and optimization of enantioselective extraction in a multi-product environment with a multistage equilibrium model [J]. Chemical Engineering and Processing, 2007, 46: 996–1005.

    Article  Google Scholar 

  11. SCHUUR B, VERKUIJL B J V, BOKHOVE J, MINNAARD A J, de VRIES J G, HEERES H J, FERINGA B L. Enantioselective liquideliquid extraction of (R,S)-phenylglycinol using a bisnaphthyl phosphoric acid derivative as chiral extractant [J]. Tetrahedron, 2011, 67: 462–470.

    Article  Google Scholar 

  12. STEENSMA M, KUIPERS N J M, de HAAN A B, KWANT G. Influence of process parameters on extraction equilibria for the chiral separation of amines and amino-alcohols with a chiral crown ether [J]. Journal of Chemical Technology Biotechnology, 2006, 81: 588–597.

    Article  Google Scholar 

  13. SCHUUR B, VERKUIJL B J V, MINNAARD A J, de VRIES J G, HEERES H J, FENRINGA B L. Chiral separation by enantioselective liquid-liquid extraction [J]. Organic Biomolecular Chemistry, 2011, 9: 36–51.

    Article  Google Scholar 

  14. TANG Ke-wen, MIAO Jia-bing, ZHOU Tao, LIU Yong-bing, SONG Li-tao. Reaction kinetics in reactive extraction for chiral separation of a-cyclohexyl-mandelic acid enantiomers with hydroxypropyl-b-cyclodextrin [J]. Chemical Engineering Science, 2011, 66: 397–404.

    Article  Google Scholar 

  15. TANG Ke-wen, ZHANG Pan-liang, PAN Chun-yue, LI Hong-jian. Equilibrium studies on enantioselective extraction of oxybutynin enantiomers by hydrophilic β-cyclodextrin derivatives [J]. Ameican Institute of Chemical Engineers Journal, 2011, 57: 3027–3036.

    Article  Google Scholar 

  16. TANG Ke-wen, CHEN Yuan-yuan, HUANG Ke-long, LIU Jia-jia. Enantioselective resolution of chiral aromatic acids by biphasic recognition chiral extraction [J]. Tetrahedron: Asymmetry, 2007, 18: 2399–2408.

    Article  Google Scholar 

  17. TANG Ke-wen, LI Hong-jian, ZHANG Pan-liang. Kinetic study on biphasic recognition chiral extraction for separation of α-cyclohexyl-mandelic acid enantiomers [J]. Journal of Chemical Technology Biotechnology, 2012, 87: 976–982.

    Article  Google Scholar 

  18. TANG Ke-wen, YI Jian-ming, LIU Yong-bing, JIANG Xin-yu, PAN Yang. Enantioselective separation of R,S-phenylsuccinic acid by biphasic recognition chiral extraction [J]. Chemical Engineering Science, 2009, 46: 4081–4088.

    Article  Google Scholar 

  19. VERKUIJL B J V, MINNAARD A J, de VRIES J G, FERINGA B L. Chiral separation of underivatized amino acids by reactive extraction with palladium-BINAP complexes [J]. Journal of Organic Chemistry, 2009, 74: 6526–6533.

    Article  Google Scholar 

  20. CHIO Y H, YANF C H, KIM H W, JUNG S. Monte Carlo simulations of the chiral recognition of fenoprofen enantiomers by cyclomaltoheptaose (β-cyclodextrin) [J]. Carbohydrate Research, 2000, 328: 393–397.

    Article  Google Scholar 

  21. CRUPI V, MAJOLINO D, MAZZAGLIA A, PACIARON A, STANCANELLI R, TOMMASINI S, VENUTI V J. Chiral recognition and complexation behaviour of b-CyD vs. L- and DL-serineby FTIR-ATR spectroscopy [J]. Journal of Molecular Structure, 2011, 993: 376–381.

    Article  Google Scholar 

  22. KOSKA J, HAYNES C A. Modelling multiple chemical equilbria in chiral partition systems [J]. Chemical Engineering Science, 2011, 56: 5853–5864.

    Article  Google Scholar 

  23. SCHUUR B, WINKELMAN J G M, HEERES H J. Equilibrium studies on enantioselective liquid liquid amino acid extraction using a cinchona alkaloid extractant [J]. Industrial and Engineering Chemistry Research, 2008, 47: 10027–10033.

    Article  Google Scholar 

  24. MEHVAR R, BROCKS D R. Stereospecific pharmacokinetics and pharmacdynamics of beta-adreergic blockers in humans [J]. Journal of Pharmaceutical Sciences, 2001, 4: 185–200.

    Google Scholar 

  25. PANDEY R K, UPADHYAY R K, KUMAR P. An asymmetric dihydroxylation route towards the synthesis of (R)-clorprenaline hydrochloride [J]. General Papers, 2006, 14: 10–14.

    Google Scholar 

  26. ZHOU Shan-shan, WANG Yan-qing, de BEER T, BAEYENS W R G, FEI Guang-tao T, DILINUER M, OUYANG Jun. Simultaneous separation of eight-adrenergic drugs using titanium dioxide nanoparticles as additive in capillary electrophoresis [J]. Electrophoresis, 2008, 29: 2321–2329.

    Article  Google Scholar 

  27. REN Xue-qin, DONG Yi-yang, HUANG Ai-jin, SUN Yi-liang, SUN Zeng-pei. Separation of the enantiomers of four chiral drugs by neutral cyclodextrin-mediated capillary zone electrophoresis [J]. Chromatographia, 1999, 49: 411–414.

    Article  Google Scholar 

  28. TANAKA Y, YANAGAWA M, TERABE S. Separation of neutral and basic enantiomers by cyclodextrin electrokinetic chromatography using anionic cyclodextrin derivatives as chiral pseudo-stationary phases [J]. Journal of High Resolution Chromatography, 1996, 19: 421–433.

    Article  Google Scholar 

  29. HIGUCHI T, CONNORS K A. Phase solubility technique [J]. Advance in Chemical Instrumentation, 1965, 653: 117–212.

    Google Scholar 

  30. TONG Sheng-qiang, YAN Ji-zhong, GUAN Yi-xin, LU You-ming. Enantioseparation of phenylsuccinic acid by high speed counter-current chromatography using hydroxypropyl-β-cyclodextrin as chiral selector [J]. Journal of Chromatography A, 2011, 1218: 5602–5608.

    Article  Google Scholar 

  31. O’BRIEN T, CROCKER L, THOMPSON R, THOMPSON K, TOMA P H, CONLON D A, FEIBUSH B, MOEDER C, BICKER G, GRINBERG N. Mechanistic aspects of chiral discrimination on modified cellulose [J]. Analytical Chemistry, 1997, 69: 1999–2007.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang, 414000, China

    Cong-shan Zhou  (周从山), Ke-wen Tang  (唐课文), Tao Yang  (杨涛), Pan-liang Zhang  (张盼良) & Zheng Zhu  (朱政)

  2. College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China

    Ping Xu  (徐萍) & Xin-yu Jiang  (蒋新宇)

Authors
  1. Cong-shan Zhou  (周从山)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ping Xu  (徐萍)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ke-wen Tang  (唐课文)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xin-yu Jiang  (蒋新宇)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tao Yang  (杨涛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Pan-liang Zhang  (张盼良)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zheng Zhu  (朱政)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Cong-shan Zhou  (周从山).

Additional information

Foundation item: Projects(21176262, 21071052) supported by the National Natural Science Foundation of China; Project supported by the Aid program for Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, China

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhou, Cs., Xu, P., Tang, Kw. et al. Enantioselective extraction of clorprenaline enantiomers with hydrophilic selector of sulfobutylether-β-cyclodextrin by experiment and modeling. J. Cent. South Univ. 21, 891–899 (2014). https://doi.org/10.1007/s11771-014-2015-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11771-014-2015-3

Key words

Search

Navigation