Liu Hui, Ding Wei
Department of Plant Protection, Northeast Agricultural University, Harbin, China.
Chirality. 2019 Mar;31(3):219-229. doi: 10.1002/chir.23050. Epub 2019 Jan 11.
Prothioconazole is a type of broad-spectrum triazole thione fungicide developed by the Bayer Company. Prothioconazole-desthio is the main metabolite of prothioconazole in the environment. In our study, enantiomeric separation of prothioconazole and prothioconazole-desthio was performed on various chiral stationary phases (CSPs) by high-performance liquid chromatography (HPLC). It was found that polysaccharide CSPs showed better ability than brushing CSPs in enantiomeric separation. The successful chiral separation of prothioconazole could be achieved on self-made Chiralcel OD, commercialized Chiralcel OJ-H and Lux Cellulose-1. Chiralpak IA, Chiralpak IB, Chiralpak IC, Chiralcel OD, Chiralpak AY-H, Chiralpak AZ-H, and Lux Cellulose-1 realized the baseline separation of prothioconazole-desthio enantiomers. Simultaneous enantiomeric separation of prothioconazole and prothioconazole-desthio was performed on Lux Cellulose-1 using acetonitrile (ACN) and water as mobile phase. In most cases, low temperature favored the separation of two compounds. The influence of the mobile phase ratio or type was deeply discussed. We obtained larger Rs and longer analysis time with a smaller proportion of isopropanol (IPA) or ethanol and more water content at the same temperature. The ratio of ACN and water had influences on the outflow orders of prothioconazole-desthio enantiomers. This work provides a new approach for chiral separation of prothioconazole and prothioconazole-desthio with a discussion of chiral separation mechanism on different CSPs.
丙硫菌唑是拜耳公司研发的一种广谱三唑硫酮类杀菌剂。丙硫菌唑-去硫代谢物是丙硫菌唑在环境中的主要代谢产物。在我们的研究中，采用高效液相色谱法（HPLC）在各种手性固定相（CSP）上对丙硫菌唑和丙硫菌唑-去硫代谢物进行了对映体分离。结果发现，多糖类手性固定相比刷型手性固定相具有更好的对映体分离能力。在自制的Chiralcel OD、商业化的Chiralcel OJ-H和Lux Cellulose-1上可成功实现丙硫菌唑的手性分离。Chiralpak IA、Chiralpak IB、Chiralpak IC、Chiralcel OD、Chiralpak AY-H、Chiralpak AZ-H和Lux Cellulose-1实现了丙硫菌唑-去硫代谢物对映体的基线分离。以乙腈（ACN）和水为流动相，在Lux Cellulose-1上对丙硫菌唑和丙硫菌唑-去硫代谢物进行了同时对映体分离。在大多数情况下，低温有利于两种化合物的分离。深入讨论了流动相比例或类型的影响。在相同温度下，异丙醇（IPA）或乙醇比例较小且水含量较高时，我们获得了更大的分离度（Rs）和更长的分析时间。ACN和水的比例对丙硫菌唑-去硫代谢物对映体的流出顺序有影响。这项工作为丙硫菌唑和丙硫菌唑-去硫代谢物的手性分离提供了一种新方法，并讨论了在不同手性固定相上的手性分离机制。
