Chen Limei, Ma Huaqiao, Liu Xia, Jiang Sheng Xiang
Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR. China.
J Chromatogr Sci. 2008 Oct;46(9):767-71. doi: 10.1093/chromsci/46.9.767.
In this paper, we describe the direct semipreparative resolution of racemic (rac)-propranolol hydrochloride by high-performance liquid chromatography using cellulose tris(3,5-dimethylphenylcarbamate) as chiral stationary phase and mobile phase systems containing petroleum ether and 2-propanol with the use of basic additives. At analytical scale, the retention factor of both enantiomers is less than 5 with the separation factor 1.95 and the resolution 2.4. Then, the analytical method is scaled up to semipreparative loading to obtain small amounts of both propranolol hydrochloride enantiomers. Petroleum ether, rather than n-hexane, is used to effectively reduce the production cost of (R)- and (S)-propranolol. To increase the throughput, overlapping injections are used, allowing an injection to be made every 6.5 min instead of every 12 min. At semipreparative scale, approximately 19 mg/h enantiomers are isolated. The first fraction [(R)-(+)-propranolol hydrochloride] is isolated with a purity of > 99.6% (e.e.) and > 97.0% yield, and the second [(S)-(-)-propranolol hydrochloride] is isolated with a purity of > 99.3% (e.e.) and > 95.0% yield. In addition, optical rotations of both propranolol hydrochloride enantiomers isolated are investigated.
在本文中,我们描述了采用高效液相色谱法,以三(3,5-二甲基苯基氨基甲酸酯)纤维素为手性固定相,含石油醚和2-丙醇并使用碱性添加剂的流动相体系,对消旋盐酸普萘洛尔进行直接半制备拆分。在分析规模下,两种对映体的保留因子均小于5,分离因子为1.95,分离度为2.4。然后,将该分析方法放大至半制备进样量,以获得少量的盐酸普萘洛尔两种对映体。使用石油醚而非正己烷,有效降低了(R)-和(S)-普萘洛尔的生产成本。为提高通量,采用重叠进样,使得进样间隔从每12分钟一次变为每6.5分钟一次。在半制备规模下,大约每小时可分离出19 mg对映体。第一个馏分[(R)-(+)-盐酸普萘洛尔]的分离纯度> 99.6%(对映体过量),收率> 97.0%,第二个馏分[(S)-(-)-盐酸普萘洛尔]的分离纯度> 99.3%(对映体过量),收率> 95.0%。此外,还对分离得到的盐酸普萘洛尔两种对映体的旋光度进行了研究。