Enantiomeric characterization of herbicide lactofen: Enantioseparation, absolute configuration assignment and enantioselective activity and toxicity

Abstract

Chiral herbicides consist of two or more enantiomers, which usually differ in their biological properties and behave enantioselectively in biochemical process. Scant studies have been published in the past decades to characterize the enantiomers of herbicide lactofen. In this study, a laboratory method was developed to prepare the lactofen enantiomers using normal phase high performance liquid chromatography with an AD-H column, and μg level production yield was achieved in a single run. The two separated enantiomers had purity of ≫99%, with their absolute configurations assigned by experimental and calculated electronic and vibrational circular dichroism. Spectral analyses including semi-empirical rules as well as comparisons with the results of quantum chemical calculations confirmed the molecular configurations of R-lactofen and S-lactofen, in this elution order. The enantioselective bioactivity toward weed (Echinochloa crusgalli) and toxicity toward aquatic algae (Microcystis aeruginosa) was assessed by measuring their growth rates after the treatments with lactofen enantiomers and racemate. The results showed that R-lactofen affected E. crusgalli more severely, while S-lactofen was more toxic to algae. Using active enantiomer instead of racemate may be more efficient and safe. Therefore, a more comprehensive understanding of the behaviors of chiral enantiomers is a need to improve activity and risk assessment and regulations of chiral compounds. Our work will be helpful to easily prepare single enantiomers from racemic mixtures and to establish effective absolute configurations of the enantiomers.