Differential Scanning Calorimetry (DSC) as a Tool for Probing the Reactivity of Polyynes Relevant to Hexadehydro-Diels–Alder (HDDA) Cascades

The differential scanning calorimetry (DSC) behavior of a number of alkyne-rich compounds is described. The DSC trace for each compound exhibits an exothermic event at a characteristic onset temperature. For the tri- and tetraynes whose [4 + 2] HDDA reactivity in solution has been determined, these onset temperatures show a strong correlation with the cyclization activation energy. The studies reported here exemplify how the data available through this operationally simple analytical technique can give valuable insights into the thermal behavior of small molecules.