Use of Retention Data as the First Step in the Identification of Cyclic Organic Peroxides in Temperature-Programmed Gas Chromatography

Temperature-programmed retention indices for eleven cyclic organic peroxides were determined by gas chromatography on slightly polar 5% biphenyl 95% dimethylpolysiloxane columns (DB-5 and Rtx-5MS) at three heating rates (5, 10, and 20° min⁻¹) from 60 to 300°C, using different chromatographs. Cyclic organic diperoxides and triperoxides had nearly constant retention indices when different heating rates and a short isothermal hold time (5 min) before the programmed increase in temperature were used. The usefulness of temperature-programmed retention indices was shown by using the data to predict the retention times and structures of unknown diperoxides or triperoxides derived from ketones. This is the first step in the identification of unknown cyclic organic peroxides, a process would otherwise require the availability of reference compounds. Revised: 7 and 17 November 2005