二茂铁衍生物在Chiralpak AD手性固定相上的对映体分离及热力学性质
Separation of Enantiomers of Ferrocenyl Derivative on Chiralpak AD and Its Thermodynamic Properties
摘 要
在直链淀粉手性固定相(Chiralpak AD)上分离了二茂铁衍生物3-(1-N,N-二甲基)乙基二茂铁的对映体.考察了醇类添加剂种类和浓度、碱的浓度对对映体分离的影响,同时探讨了手性识别机理.结果发现:乙醇是最佳醇类添加剂,并且在流动相中加入少量碱有助于改善峰形,增加分离度.通过改变温度求出相应的拆分过程中热力学参数,这些参数表明在所研究温度范围内,Chiralpak AD对该溶质的分离过程为焓控过程,高温对分离不利.
手性识别机理
二茂铁
对映体
热力学
焓控
Chiral stationary phase
Mechanism of chirality recognition
Enantiomers
Ferrocene
Thermodynamics
Enthalpy control process
Abstract
Enantiomers of a ferrocenyl derivative,i.e.3-(1-N,N-dimethyl) ethyl ferrocene,were separated on the Chiralpak AD column (250 mm×4 mm,5 μm).Factors influential to the separation,including kinds and concentration of alcohol as denaturant added to the mobile phase and concentration of base in the mobile phase,were studied,and the mechanism of recognition of chirality was discussed.It was found that ethanol was the best additive,and that addition of small amount of triethylamine was profitable to improve the peak shape and rate of separation.By changing the temperature during the separation process,relative thermodynamic parameters were found,which indicated that within the range of temperatures studied,an enthalpy control process of Chiralpak AD against the separation of the solute was observed.Too high a temperature was unfavourable.
中图分类号 O657.37
所属栏目 试验与研究
基金项目 云南省自然科学基金(2007B220M)资助项目
收稿日期 2008/1/11
修改稿日期
网络出版日期
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备注沈报春(1974-),女,云南人,副教授,博士,研究方向为手性药物对映体分离.
引用该论文: SHEN Bao-chun,YUAN Jian-yong,WANG Heng-chun,XU Bei-jia,XU Xiu-zhu. Separation of Enantiomers of Ferrocenyl Derivative on Chiralpak AD and Its Thermodynamic Properties[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2008, 44(11): 1017～1020
沈报春,袁建勇,王恒春,徐贝佳,徐秀珠. 二茂铁衍生物在Chiralpak AD手性固定相上的对映体分离及热力学性质[J]. 理化检验－化学分册, 2008, 44(11): 1017～1020
被引情况:
【1】陈建波,毛健伟,吴爱娟, "手性固定相-高效液相色谱法分离噁唑菌酮对映异构体",理化检验－化学分册 49, 1483-1485(2013)
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参考文献
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【2】Wang T,Chen Y W,Vailaya A.Enantiomeric separation of some pharmaceutical intermediates and reversal of elution orders by high-performance liquid chromatography using cellulose and amylose tris (3,5-dimethylphenylcarbamate) derivatives as stationary phases[J].Journal of Chromatography A,2000,902:345-355．
【3】Magora A,Abu-Lafi S,Levin S.Comparison of the enantioseparation of racemic uridine analogs on Whelk-O 1 and ChiralPak-AD columns[J].Journal of Chromatography A,2000,866:183-194．
【4】Watt A P,Hitzel L,Mortishire-Smith R J.Enantiomeric separation of substituted 2-arylindoles on derivatised polysaccharide chiral stationary phases[J].J Biochem Biophys Methods,2002,54:275-286．
【5】Chankvetadze B,Kartozia I,Yamamoto C,et al.Comparative enantioseparation of selected chiral drugs on four different polysaccharide-type chiral stationary phases using polar organic mobile phases[J].Journal of Pharmaceutical and Biomedical Analysis,2002,27:467-478．
【6】张红丽,李晓燕,柳春辉,等.高效液相色谱法拆分雷喏嗪[J].分析测试技术与仪器,2004,10(3):151-153．
【7】Yamamoto C,Yashima E,Okamoto Y.Structural Analysis of Amylose Tris (3,5-dimethylphenylcarbamate) by NMR Relevant to Its Chiral Recognition Mechanism in HPLC[J].J Am Chem Soc,2002,124:12583-12589．
【8】Togni A,Bieler N,Burckhardt U,et al.Recent studies in asymmetric catalysis using ferrocenyl ligands[J].Pure Appl Chem,1999,71:1531-1537．
【9】Okamoto Y,Kaida Y.Resolution by high-performance liquid chromatography using polysaccharide carbamates and benzoates as chiral stationary phases[J].Journal of Chromatography A,1994,666:403-419．
【10】Wainer I W,Shibata R M S.Resolution of enantiomeric aromatic alcohols on a cellulose tribenzoate high-performance liquid chromatography chiral stationary phase: A proposed chiral recognition mechanism[J].Journal of Chromatography A,1987,411:139-151．
【11】Francotte E,Wolf R M,Lohmann D,et al.Chromatographic resolution of racemates on chiral stationary phases:I.Influence of the supramolecular structure of cellullose triacetate[J].Journal of Chromatography A,1985,347:25-37．
【12】Okamoto Y,Yashima E.Polysaccharide derivatives for chromatographic separation of enantiomers[J].Angewandte Chemie International Edition,1998,37:1020-1043．
【13】Weng W,Wang Q H,Yao B X,et al.Enantioseparation of amino acid derivatives on an immobilized network polymer derived from -tartaric acid[J].Journal of Chromatography A,2004,1042:81-87．
【14】Oberleitner W R,Maier N M,Lindner W.Enantioseparation of various amino acid derivatives on a quinine based chiral anion-exchange selector at variable temperature conditions.Influence of structural parameters of the analytes on the apparent retention and enantioseparation characteristics[J].Journal of Chromatography A,2002,960:97-108．
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