In this thesis, the results of synthesis of chiral ionic liquids (ILs) and an investigation of their application in chiral separation and catalysis are described. The study of the chiral lLs application was performed using liquid-liquid extraction, crystallization and asymmetric catalysis with analysis of substrate content and enantioselectivity by High Performance Liquid Chromatography (HPLC) . A series of chiral lLS with chiral cations or chiral anions were synthesized through alkylation or anion exchange with optical pure starting materials as the •chiral pool", Properties of chiral ILS made in house were studied using various techniques, The structures and configurations of the chiral ILs can be altered easily to meet the required physical properties, such as melting point and viscosity, Chiral! ILs made in house show chiral affinity with a range of racemic compounds, In the liquid-liquid extraction of menthol from chiral lL, good extraction is observed from the chiral lL layer into alkane !layer without visible leaching of the chiral lL into the alkane layer. In the mandelic acid resolution by • Dutch resolution", 22 different ILS were used as additive in the chiral selector, In general, ILS exhibit a equalize effect on both yield and ee of the final product. For the asymmetric catalysis study, both Mukaiyama-aldol reaction and Diels-Alder reaction were investigated with Cu(II)-PhBOX and Zn(II)-PhBOX as catalyst. In the Mukaiyama-aldol reaction, chiral ILS can be applied . as ligand and an increased ee is observed as compared with the reactions in the absence of the Il. In the Diels-Alder reaction, addition of the chiral Il 19 (Il of (1R,2S.5R)- menthol) with Zn(II)-PhBOX led to an increase in the endo ee from 5 % in DCM, 68 % in ether and 57 % in pure (C 2mim][NH 10 91 % under homogeneous reaction condition and 95 % in biphasic system with both high conversion and high endo selectivity. The endo selectivity of biphasic system with the chiral lL 1 g, [C2mim][NTf21 and ether is 99 %, which means nearly all product goes into endo form with 95 % ee.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:603555 |
| Date | January 2013 |
| Creators | Wang, Ying |
| Publisher | Queen's University Belfast |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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