Analysis of alkylpyrrole autoxidation products by high-performance liquid chromatography with thermospray mass spectrometry and UV photodiode-array detection.

A method employing high-performance liquid chromatography with thermospray mass spectrometry (TSP-MS) and photodiode-array detection was developed and applied to the analysis of autoxidation products of 2,5-dimethyl-N-alkylpyrroles in aqueous solution under air or 18O2. Numerous oxidation products were separated, characterized and categorized, primarily as (1) non-polar oligomers without incorporated oxygen, and (2) polar, oxygen-containing monomers. Kinetic studies showed that oligomerization was the dominant autoxidation pathway, with production of unstable dimers and trimers and, ultimately, a high-molecular-mass sediment. TSP-MS together with UV and proton nuclear magnetic resonance spectral data revealed that both the dimer and trimer contained a novel methylene bridge. These results suggest that this method is suitable for the analysis of alkylpyrrole autoxidation products that may be relevant to hexane neuropathy and products that are responsible for the instability of fuels in storage.