title: Isolation and identification of the metolachlor stereoisomers using high-performance liquid chromatography, polarimetric measurements, and enantioselective gas chromatography.
abstract: Because of the presence of two chiral elements (an asymmetrically substituted carbon and a chiral axis), the herbicide metolachlor consists of four stereoisomers stable at ambient temperature with aSS-, aRS-, aSR-, and aRR-configurations (aSS, the isomer with aS,1'S-configuration, etc.). Metolachlor, initially introduced into the market as the racemic product containing all four stereoisomers, is currently being replaced worldwide by S-metolachlor, the product enantiomerically enriched with the herbicidally active 1'S-isomers (aSS, aRS). The isomer-specific analysis of metolachlor requires not only enantioselective ("chiral") analytical techniques but also suitable reference compounds. In this study, two of the four metolachlor isomers were isolated from rac-metolachlor in enantio- (ee > 98%) and diastereomerically pure forms by a combination of achiral and chiral high-performance liquid chromatography (HPLC). The two isomers were identified as the aSS- and the aRR-isomers by polarimetric measurements, in reference to previous data. The two isomers were then thermally equilibrated to 1:1 mixtures of the aSS/aRS and aRR/aSR diastereomers, respectively, so that analytical data of all four metolachlor isomers became available; they were then used to identify these isomers in technical products by chiral high-resolution gas chromatography (HRGC). The kinetics of the thermally induced interconversion of the atropisomers was studied and the consequences, such as for GC analysis, are discussed. A comparison of on-column and split/splitless injection indicated that the latter technique results in significant isomerization prior to separation and, therefore, cannot be used for accurate isomer analysis.
authors.affiliation: Swiss Federal Research Station, CH-8820 Wädenswil, Switzerland.
authors.forename: M D
authors.initials: MD
authors.lastname: Müller
authors.forename: T
authors.initials: T
authors.lastname: Poiger
authors.forename: H
authors.initials: H
authors.lastname: Buser
mesh_terms: D000081:Acetamides / Q000032:analysis* / Q000737:chemistry; D002849:Chromatography, Gas / Q000379:methods*; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D004785:Environmental Pollutants / Q000032:analysis; D008401:Gas Chromatography-Mass Spectrometry; D006540:Herbicides / Q000032:analysis*; D006358:Hot Temperature; D007700:Kinetics; D010573:Pesticide Residues / Q000032:analysis; D013237:Stereoisomerism
chemical_list: D000081:Acetamides; D004785:Environmental Pollutants; D006540:Herbicides; D010573:Pesticide Residues; C051786:metolachlor