Abstract
The very low pressure pyrolysis of trans-decalin (⩽1450 K, 10 −3 s, 10 −5 mbar) has been studied under real-time conditions by mass spectrometry. The results obtained confirm the existence of several unimolecular reaction pathways: (i) CC bond ruptures (not only the preferential transannular CC cleavage); thereupon, (ii) a reaction course resulting in olefinic C/H isomeric hydrocarbons; and subsequently, (iii) thermal conversion of these reaction intermediates formed via routes (i) and (ii). The observed reaction pattern for the decomposition of decalin is similar to that for the thermal rearrangement of cyclohexane.
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