利用Chiralpak AS-H手性色谱柱,以正己烷为流动相,以有机醇为极性改性剂,采用正相高效液相色谱法分别对乙草胺和异丙草胺的对映体进行了手性拆分,并结合紫外-可见、圆二色、旋光检测器和八区律规则对其对映体的绝对构型进行了判定。结果表明:乙草胺和异丙草胺的第一洗脱峰在220nm检测波长下均具有负的康顿(Cotton)效应和旋光(ORD)信号,根据八区律判定其构型为aR-型,具有相反信号的第二洗脱峰为aS-型。以正己烷-异丙醇(97∶3,体积比)为流动相时,乙草胺和异丙草胺分离度分别为2.23和1.52。其手性拆分过程均受焓驱动,且分子中的N-烷氧取代基在对映体与手性固定相作用过程中具有重要作用。
The enantiomers of acetochlor and propisochlor were separated using high performance liquid chromatography with a Chiralpak AS-H column.The mobile phase was n-hexane with organic alcohols as polar modifiers.Absolute configurations of the enantiomers were identified by a combination of UV-Vis,Cirular Dichroism,ORD detector and the octant rule.The results showed that the first eluted peak for both acetochlor and propisochlor had the negative cotton effect and showed(-) ORD signal at 220 nm corresponded to aR-isomer.Baseline enantiomeric separation of acetochlor and propisochlor was achieved with mobile phase of n-hexane-isopropyl alcohol(97∶3 by volume).Moreover,the enantiomeric resolution was controlled by enthalpy term,in which the N-alkoxyalkyl substituents played important roles.