填充柱超临界CO_2流体色谱制备拆分4种外消旋γ-内酯香料

Preparative Resolution of Four Racemic γ-Lactone Flavors by Packed Column Supercritical CO_2 Fluid Chromatography

填充柱超临界CO2流体色谱是近年发展的一种绿色高效色谱分离技术。本文采用填充柱超临界CO2流体色谱对外消旋γ-辛内酯、γ-癸内酯、γ-十一内酯、γ-十二内酯4种香料进行制备规模手性拆分。色谱柱Chiralpak AD 250mm×10mm10μm,柱温、柱压、改性剂等参数在前期分析研究基础上设定。调节流动相流速、样品浓度得较佳分离通量,并进行制备性分离,结果:γ-辛内酯,上样2mg/次,每次运行9min,180min分离40mg,回收率(以2个对映体计,下同)66.3%;γ-癸内酯,上样0.8mg/次,每次运行9min,180min分离16mg,回收率68.1%;γ-十一内酯,上样0.8mg/次,每次运行11min,220min分离16mg,回收率64.4%;γ-十二内酯,上样0.7mg/次,每次运行11min,220min分离14mg,回收率71.4%。上述分离制备所得对映体的光学纯度(e.e%)均为100%。

Packed column supercritical CO2 fluid chromatography （pSFC） is a recently developed environment friend- ly and high efficieney separation technique. In this paper, pSFC was employed for preparative resolution of four racemic flavors of γ-octalaetone, γ-deealactone, γ-undeealactone and γ-dodecalaetone. The column temperature, column pressure and modifier were selected on the basis of previous analytical pSFC separation. The column used was Chiralpak AD 250×10 mm 10μm. The throughput to conduct the preparative separation was optimized by varying flow rate of mobile phase and sample concentration loaded. The best results for separation were accomplished as follows： γ-octalactone, 2 mg load- ed per run of 9 min, total of 40 mg resolved in 180 min with the recovery being 66.3%（enantiomers weighed together）; γ-decalactone, 0.8 mg loaded per run of 9min, total of 16mg resolved in 180min with the recovery being 68.1%; γ- undecalactone, 0.8 mg loaded per run of 11 min, total of 16 mg resolved in 220min with the recovery being 64.4%; γ- dodecalactone, 0.7 mg loaded per run of 11 min, total of 14mg resolved in 220 min with the recovery being 71.4%. The enantiomers obtained from the above preparative resolutions were all in an optical purity of 100% e. e.