Sadutto Daniele, Ferretti Rosella, Zanitti Leo, Casulli Adriano, Cirilli Roberto
Dipartimento del Farmaco, Istituto Superiore di Sanità, Viale Regina Elena 299, I-00161 Rome, Italy.
Dipartimento di Malattie Infettive, Parassitarie ed Immunomediate, Istituto Superiore di Sanità, Viale Regina Elena 299, I-00161 Rome, Italy.
J Chromatogr A. 2016 May 6;1445:166-71. doi: 10.1016/j.chroma.2016.04.011. Epub 2016 Apr 4.
Direct HPLC separation of enantiomers of Bicalutamide (BCT), a non-steroidal antiandrogen used for the treatment of prostate cancer, was performed by using the immobilized amylose-based Chiralpak IA chiral stationary phase (CSP). Enantioselective conditions were achieved using standard normal phase mixtures n-hexane-alcohol (ethanol or 2-propanol) and a "non-standard" mobile phase containing ethyl acetate (EA). The chromatographic behaviour of the IA CSP under these elution modes was evaluated and compared at different temperatures. The eluent mixture n-hexane-EA-ethanol 100-30-5 (v/v/v) and the column temperature of 40°C were identified as the best operational conditions to carry out semipreparative enantioseparations on a 1-cm I.D. IA column. Using this protocol, about 960mg of (R)-BCT, which is the enantiomer with the almost entire anti-androgenic activity of BCT, per day could be isolated. The analytical and semipreparative HPLC resolution of chiral impurities of BCT, and their empiric absolute configuration assignment by circular dichroism correlation method are also presented.
比卡鲁胺(BCT)是一种用于治疗前列腺癌的非甾体类抗雄激素药物,采用基于直链淀粉的手性固定相Chiralpak IA,通过高效液相色谱法(HPLC)直接分离其对映体。使用标准正相混合物正己烷 - 醇(乙醇或异丙醇)以及含有乙酸乙酯(EA)的“非标准”流动相实现对映体选择性条件。在不同温度下评估并比较了IA手性固定相在这些洗脱模式下的色谱行为。已确定洗脱剂混合物正己烷 - EA - 乙醇100 - 30 - 5(v/v/v)和40°C的柱温是在1厘米内径的IA柱上进行半制备对映体分离的最佳操作条件。按照此方案,每天可分离出约960毫克(R)-BCT,它是几乎具有BCT全部抗雄激素活性的对映体。还介绍了比卡鲁胺手性杂质的分析和半制备HPLC分离度,以及通过圆二色性相关方法对其经验性绝对构型的归属。