Chiral extraction of ketoprofen enantiomers with chiral selector tartaric esters

Distribution behavior of ketoprofen enantiomers was examined in methanol aqueous and organic solvent mixture containing tartaric esters. The influence of length of alkyl chain of tartaric esters, concentration of L-tartaric esters and methanol aqueous, kind of organic solvent on partition ratio and separation factors was investigated. The results show that L-tartaric and D-tartaric esters have different chiral recognition abilities. S-ketoprofen is easily extracted by L-tartaric esters, and R-ketoprofen is easily extracted by D-tartaric esters. L-tartaric esters form more stable diastereomeric complexes with S-enantiomer than that with R-enantiomer. This distribution behavior is consistent with chiral recognition mechanism. With the increase of the concentration of tartaric ester from 0 to 0.3 mol/L, partition coefficient K and separation factor a increase. Also, the kind of organic solvent and the concentration of the methanol aqueous have significant influence on K and a.

Resolution of α-cyclohexyl-mandelic acid enantiomers by two-phase (O/W) recognition chiral extraction

This paper presents a new chiral separation technology:two-phase(O/W)recognition chiral extraction.Distribution behavior of alpha-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-isobutyl tartrate in 1,2-dichloroethane organic phase and beta-CD derivatives in aqueous phase,and the influence of the kind and concentration of extractant and pH on extraction performance was investigated.The experimental results indicate that two-phase(O/W)recognition chiral extraction is of strong chiral separation ability.HP-^-CD,HE-beta-CD and Me-beta-CD have higher recognition ability for S-CHMA than that for R-CHMA,among which HP-beta-CD has the strongest ability;whereas,D-isobutyl tartrate has reversed recognition ability for them.In the extraction system containing HP-beta-CD and D-isobutyl tartrate,e.e.% of S-CHMA in aqueous phase reached 27.6% by one stage extraction,and the distribution ratio for R-CHMA(k_R)and for S-CHMA(k_S)and separation factor(alpha)are 2.44,0.89 and 2.49,respectively.Meanwhile,pH and concentration of extractant have great effects on chiral separation ability.Two-phase(O/W)recognition chiral extraction has great significance for preparative separation of racemic compounds.

Study on extraction kinetics ofα-cyclopentylmandelic acid enantiomers with hydroxyethyl-β-cyclodextrin as chiral selector

In this work,the kinetic study on reactive extraction ofα-cyclopentylmandelic acid(α-CPMA)enantiomers was performed in a Lewis cell using hydroxyethyl-β-cyclodextrin(HE-β-CD)as chiral selector.The enantioselective complexation equilibrium between HE-β-CD andα-CPMA enantiomers was studied by phase solubility method.The important process parameters affecting the initial extraction rate were separately studied and the reaction rate equations were deduced.The optimal conditions for kinetic study were as follows:stirring speed of 75 r·min^(-1),interfacial area of 12.56 cm^2,pH of 2.5,initial HE-β-CD concentration of 0.05 mol·L^(-1),initialα-CPMA concentration of 5 mmol·L^(-1),and temperature of 278 K.The reaction has been found to be first order inα-CPMA and second order in HE-β-CD with the forward rate constants of 2.056×10^(-3)m^6·mol^(-2)·s^(-1)and 1.459×10^(-3)m^6·mol^(-2)·s^(-1)for(S)-α-CPMA and(R)-α-CPMA,respectively.The complexation equilibrium constants were evaluated as 61 L·mol^(-1) and 117 L·mol^(-1)for(S)-α-CPMA and(R)-α-CPMA,and the intrinsic enantioselectivity is estimated as 1.92.