A simple criterion for gas chromatography/mass spectrometric analysis of thermally unstable compounds, and reassessment of the by-products of alkyl diazoacetate synthesis

RATIONALE A principal limitation of gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS) is the thermal instability of analytes. We propose that the injector and column temperatures should not exceed the atmospheric pressure boiling point, without decomposition, of the highest homologue of the series being analyzed, instead of the time‐consuming procedure of obtaining chromatograms using different temperatures. METHODS A series of thermally unstable diazocarbonyl compounds, alkyl diazoacetates (predicted limit of stability approx. 140 °C, the boiling point of ethyl diazoacetate), was selected for GC/MS analysis using standard equipment. Different GC separation conditions were selected so that the retention temperatures of target compounds were both below and above 140 °C. RESULTS Analyzing alkyl diazoacetates within their thermal stability range permitted reanalysis of their typical synthesis by‐products. No dialkyl fumarate or maleate impurities, principal decomposition products which have often been reported previously, were found. Instead, alkyl esters of glycolic acid nitrate, O2NOCH2CO2R, and 'pseudo‐dimeric' products, ROCO[C2H3NO]CO2R, were discovered for the first time. CONCLUSIONS Avoiding the decomposition of thermally unstable organic compounds during GC and/or GC/MS analysis requires estimating their degradation temperature limits. This limit can be estimated as being equal to the atmospheric pressure boiling point of the highest homologue in the homologous series under consideration that does not decompose on boiling. Copyright © 2012 John Wiley & Sons, Ltd.