Acylation of chiral alcohols: a simple procedure for chiral GC analysis

Abstract

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

The authors are grateful to the Secretaría de Estado de Política Científica y Tecnológica of the Spanish Ministerio de Ciencia y Tecnología (CTQ2009-14699-C02-01) and Departament d’Universitats, Recerca i Societat de la Informació of the Generalitat de Catalunya (2001SGR00309) for financial support. M. Oromi-Farrús thanks the Ministerio de Educación y Cultura for the Predoctoral Fellowship no. AP 2001–3761.