乙草胺和异丙草胺对映异构体的拆分

顾芳; 张晓翔; 夏婷婷; 陈景文; 蔡喜运

乙草胺和异丙草胺对映异构体的拆分

1.
大连理工大学环境学院工业生态与环境工程教育部重点实验室,辽宁大连 116024
2.
浙江建安检测研究院有限公司卫生评价中心,杭州 310000

基金项目:

国家自然科学基金(20707002);霍英东教育基金(114042)资助题目.

计量
- 文章访问数: 1594
- HTML全文浏览量: 70
- PDF下载量: 418
- 被引次数: 0
出版历程
- 收稿日期: 2010-12-10
- 修回日期: 2011-05-03

Enantiomeric resolution and thermodynamical mechanism of acetochlor and propisochlor

1.
Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education/Department of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, Liaoning Province, China
2.
Department of Health Evaluation, Zhejiang Giian Test Institute CO., LTD, Hangzhou 310000, China

摘要

摘要: 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220 nm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。
- 高效液相色谱 /
- 手性固定相 /
- 对映体拆分 /
- 乙草胺 /
- 异丙草胺
Abstract: 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.
- high performace liquid chromatography /
- chiral stationary phase /
- enantiomeric resolution /
- acetochlor /
- propisochlor

HTML全文

参考文献(23)

HUA Ri-mao(花日茂),YUE Yong-de(岳永德),FAN De-fang(樊德方).乙草胺在水中的光化学降解[J].Chin J Pestic Sci(农药学学报),2000,3(1):71-74.

WANG Xian-feng(王险峰),GUANG Cheng-hong(关成宏).异丙草胺使用技术[J].Chin J Pestic(农药),2000,39(6):39-40.

WANG Y S,TAI K T,YEN J H.Separation,bioactivity,and dissipation of enantiomers of the organophosphorus insecticide fenamiphos[J].Ecotoxicol Environ Saf,2004,57(3):346-353.

SANCHEZ-RASERO F,MATALLO M B,DIOS G,et al.Simultaneous determination and enantiomeric resolution of mecoprop and dichlorprop in soil samples by high-performance liquid chromatography and gas chromatography-mass spectrometry[J].J Chromatogr A,1998,799(1-2):355-360.

QIU Jing(邱静),LI Li(李莉),ZHOU Zhi-qiang(周志强).高效液相色谱对氯氟吡乙酸1-甲基庚酯对映体的拆分 [J].Chin J Pestic Sci(农药学学报),2002,4(2):67-70.

YANG Li(杨丽),JIANG Shu-ren(江树人),LIAO Yong(廖勇),et al.流动相添加剂法与手性固定相法对己唑醇光学异构体的拆分[J].Chin J Pestic Sci(农药学学报),2004,6(2):90-92.

YANG Li-ping(杨丽萍),LI Shu-zheng(李树正),LI Yu-chang(李煜昶),et al.三种三唑类杀菌剂对映体生物活性的研究[J].Chin J Pestic Sci(农药学学报),2002,4(2):67-70.

WANG Peng(王鹏),JIANG Shu-ren(江树人),ZHOU Zhi-qiang(周志强),et al.乙草胺的对映体识别[J].Chin J Pestic(农药),2005,44(3):113-114.

TIAN Q,LV C G,ZHOU Z Q,et al.Enantiomeric separation of chiral pesticides by high performance liquid chromatography on cellulose tris-3,5-dimethyl carbamate stationary phase under reversed phase conditions[J].J Sep Sci,2007,30(3):310-321.

MVLLER M D,BUSER H R.Environmental behavior of acetamide pesticide stereoisomers[J].Enviro Sci Technol,1995,29(8):2023-2030.

LIGHTNER D A.Determination of absolute configuration by CD.Applications of the octant rule and the exciton chirality rule[J].Techniques and Instrumentation in Analytical Chemistry,1994,14:131-174.

MVLLER M D,POIGER T,BUSER H R.Isolation and identification of the metolachlor stereoisomers using high-performance liquid chromatography,polarimetric measurements,and enantioselective gas chromatography[J].J Agric Food Chem,2001,49(1):42-49.

WANG T,ROBERT M,WENSLOW J.Effects of alcohol mobile-phase modifiers on the structure and chiral selectivity of amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase[J].J Chromatogr A,2003,1015(1-2):99-110.

OKAMOTO M.Reversal of elution order during the chiral separation in high performance liquid chromatography[J].J Pharm Biomed Anal,2002,27(3-4):401-407.

CHEN Ping(陈平),NA Peng-jun(纳鹏君),HAN Xiao-qian(韩小茜),et,al.禾草灵对映异构体在高效液相色谱手性固定相上的拆分[J].Chin J Inst Anal(分析测试学报),2003,5(3):39-41.

WANG Peng(王鹏),JIANG Shu-ren(江树人),FENG Nan(冯楠),et al.醇改良剂对两种手性农药对映体拆分的影响[J].Chin J Inst Anal(分析测试学报),2005,9(5):104-106.

SUN Yu-qing (孙毓庆),HU Yu-zhu (胡育筑).HPLC Solvent System to Choose and Optimization(液相色谱溶剂系统地选择与优化)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),2008.

WANG P,JIANG S R,ZHOU Z Q,et al.Enantiomeric resolution of chiral pesticides by high-performance liquid chromatography[J].J Agric Food Chem,2006,54(5):1577-1583.

ZHOU Ying(周瑛),ZHANG Shi-hao(张世浩),LIU Wei-ping(刘维屏),et al.敌草胺对映体的高效液相色谱分离及手性拆分热力学研究[J].Chin J Pestic Sci(农药学学报),2006,8(3):260-294.

BERTHOD A.Chiral recognition mechanisms[J].Anal Chem,2006,78(7):2093-2099.

O’BRIEN T,CROCKER L,THOMPSON R,et al.Mechanistic aspects of chiral discrimination on modified cellulose[J].Anal Chem,1997,69(11):1999-2007.

HOU Jing-guo(侯经国),MEN Xiao-rong(孟晓荣),HE Tian-xi(何天稀),et al.农药甲霜灵对映体的高效液相色谱分离及手性拆分热力学研究[J].Chin J Anal Chem(分析化学),2003,31(3):307-310.

OBERLEITNER W R,MAIER N M,LINDNER W.Enantioseperation of various amino acid derivations on a quinine based chiral anion-exchange selector at variable temperature conditions[J].J Chromatogr A,2002,960(1-2):97-108.

施引文献

资源附件(0)

访问统计