High-performance liquid chromatographic separation of enantiomeric amines

Summary Separations of twelve different racemic amines were studied by high-performance liquid chromatography (HPLC) in several column-solvent combinations. Relative retentions, which show some dependence upon the substitution at the asymmetric centers, are reported for the amines which were examined as the (+)-10-camphorsulfonamides.     

丙炔醇类和丙二烯醇类化合物对映体的气相色谱拆分

使用全甲基-β-环糊精柱(Rt-βDex^TM~cst柱),对5种丙炔醇类和4种丙二烯醇类化合物对映体的气相色谱分离方法进行了研究,结果4种丙炔醇类和4种丙二烯醇类对映体得到分离,分离因子α为1.01～1.04,分离度R一般大于1.5。方法已用于实际不对称合成样品ee值的测定。探讨了对映体在该柱上的拆分机理,认为烷基取代基适当的疏水性和大小是降低非特异性相互作用、形成相对稳定的不对称环糊精包合物,从而成功拆分光学活性异构体的关键。     

Gas chromatographic separation of some labelled aromatic halogen compounds

Gas—liquid-chromatographic techniques for the separation of a large variety of mono-, di-and polysubstituted benzene derivatives from their multicomponent systems have been developed for the study of reactions of recoil halogen atoms with aromatic compounds. The¹⁸F,^34mCl,³⁸Cl,⁸²Br and¹²⁸I labelled benzene derivatives were produced by neutron irradiations of the corresponding liquid mixtures. Because of the short half-life of most of the isotopes in question a relatively fast method was required, therefore each of the techniques described takes less than one hour to achieve the separation.     

Cyclodextrin-based liquid chromatographic enantiomeric separation of chiral dihydrofurocoumarins, an emerging class of medicinal compounds

A set of 28 racemic dihydrofurocoumarins in which the stereogenic center is located in the furan ring have been synthesized. Currently no effective asymmetric synthesis of this class of compounds exists, although their enantiomers are produced biologically by certain plants. Their diverse medicinal properties are being investigated in several laboratories. The enantioselective separation of these dihydrofurocoumarins by three native and six derivatized cyclodextrins has been evaluated in the reversed-phase mode, the polar organic mode, and normal-phase mode. The hydroxypropyl-beta-cyclodextrin is the most effective chiral stationary phase (CSP) at separating the dihydrofurocoumarins into enantiomers, showing some enantioselectivity for 22 dihydrofurocoumarins, and baseline resolving 16 of the 28 compounds in the reversed-phase mode. The acetyl-beta-cyclodextrin and 2,3-dimethyl-beta-cyclodextrin also showed enantioselectivity for a large number (18 and 17, respectively) of dihydrofurocoumarins in the reversed-phase mode. The native cyclodextrins are ineffective and the aromatic derivatized beta-cyclodextrins are only marginally effective at separating the furocoumarin enantiomers in the reversed-phase mode. The polar organic mode and the normal-phase mode have also been evaluated with these CSPs, but no enantioseparations were observed.     

Enthalpy-entropy compensation effect in gas chromatographic enantiomeric separation

In this paper, the enthalpy-entropy compensation effect in the enantiomeric separation by modified cyclodextrins (CD) and diamide chiral stationary phase (CSP) gas chromatography was investigated using the method of plotting △(△H) versus △(△G) rhm combined with t-test statistic analysis. The investigated racemates cover α-phenylethylamine and its analogs, 2-alkylamines, chiral acyclic alcohols, halogenated arylethanediol-1, 2-diperfluoropropionates, amino acid and its analogs, and two series of compounds containing chloro and bromo substituents. From the compensation analysis results, the effects of the diluent composition in the investigated chiral stationary phases, the size and the modified groups on investigated cyclodextrins, the derivatization methods and the groups attached to the stereocenters on enantiomeric separation mechanisms were all discussed.     

Gas chromatographic separation of the enantiomers of flumecinol and some related compounds

Flumecinol and related compounds can, without derivatization, be separated into their enantiomers by gas chromatography on cyclodextrin phases; permethylated β-cyclodextrin dissolved in OV-1701 can be particularly recommended. Thermodynamic data describing the different intensities of interaction of the individual enantiomers with the stationary phases were determined. The values measured imply different separation mechanisms for the compounds investigated.     

Direct high-performance liquid chromatographic separation of enantiomeric peptidoleukotriene antagonists.

Enantiomeric peptidoleukotriene antagonists, SK&F R-106203 and SK&F S-106203 can be effectively separated on a cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase. The utility of this chiral high-performance liquid chromatographic method in assigning absolute stereochemistry to SK&F S-106203-Z2, a non-crystalline amorphous compound which is not amenable to single crystal X-ray analysis, is demonstrated by correlation with the absolute configuration determined crystallographically for a second salt form.     

Gas chromatographic separation of substituted pyridines

Capillary gas chromatographic methodology for separation of complex mixtures of substituted pyridines has been demonstrated on polar (CAM) and non-polar (DB-5) columns. Separations are characterized by high resolution, high sensitivity, a wide dynamic detector range, and good reproducibility. For the first time, Kováts retention indices have been calculated for pyridine and substituted pyridines. Correlations of retention indices with physico-chemical properties, such as hydrogen bonding, pyridine pKa and Hammett substituent constants are discussed.     

Combinatorial enantiomeric separation of diverse compounds using capillary array electrophoresis

Combinatorial chiral separations were performed on a 96-capillary array electrophoresis system. A comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral and acidic compounds was developed. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pK and structures. Therefore, unknown compounds can be screened in this manner to identify the optimal enantioselective conditions in just one run.     

Gas chromatographic separation of low-boiling pyridine bases

Summary The gas chromatography of the -picolines in a lowboiling tar base fraction, is described. The methods developed employ packed columns with binary phases containing N,N,N,N-tetrakis(2-hydroxypropyl) ethylenediamine plus metal transition stearate, or with a ternary phase containing this mixture and o-hydroxyethylresorcinol