Epimerization of Cypermethrin Stereoisomers in Alcohols

Abstract

Isomerization induced by light, heat, and organic solvents has been shown to occur for some pyrethroid insecticides. Alcohols are popular solvents that are used in sample extraction, storage, and analysis. Thus, alcohol-induced epimerization may contribute to the incorrect interpretation of results from enantioselective chemical analysis and bioassay of pyrethroids like cypermethrin. In this study, we investigated the relationship between the rate of epimerization of cypermethrin stereoisomers: 1R-cis-alphaR and 1R-trans-alphaR and short-chain alkyl alcohol properties. In this study, complete epimerization of 1R-cis-alphaR produced an almost equal fraction of 1R-cis-alphaS, and that of 1R-trans-alphaR yielded 1R-trans-alphaS. For both stereoisomers, epimerization was most rapid in ethanol. The same stereoisomers underwent relatively rapid epimerization in methanol, n-propanol, 2-methyl-1-propanol, and n-butanol but were stable in 2-butanol, suggesting that secondary alcohols have reduced reactivity, likely due to steric hindrance. We further evaluated epimerization of 1R-cis-alphaR and 1R-trans-alphaR stereoisomers of cypermethrin as a function of water content in methanol. The presence of water in methanol generally increased the epimerization rate. For 1R-cis-alphaR, epimerization was most rapid with a water content of < or =2%, while for 1R-trans-alphaR, epimerization was most rapid with a water content of 10%. Results from this study clearly show that contact with commonly used primary alcohols may result in rapid abiotic epimerization, underscoring the importance of considering configurational stability in ensuring the analytical integrity and correct interpretation of bioassay data for stereoisomers of cypermethrin and similar pyrethroids.