The alternative thermal decomposition mode of 2-oxetanone and 2-azetidinone: a DFT and PES study

Abstract We have found that, while 2-oxetanone undergoes thermal decarboxylation at 350°C to give CO 2 and ethene, 2-azetidinone proceeds in two different modes at 550°C, giving isocyanic acid, ethene, ketene, hydrogen cyanide and carbon monoxide among the pyrolysis products. B3LYP/6-31G ** calculations were performed to investigate the two alternative cycloreversion pathways for the two compounds. Theoretical thermodynamic data predicted that decarboxylation of 2-oxetanone has among the lowest activation barrier (159 kJ mol −1 ) and free energy (Δ G =−183 kJ mol −1 ). While the cycloreversion to ethene can be classified as a concerted asynchronous process, natural bond orbital (NBO) analysis suggested that the cycloreversion to ketene is more asynchronous for 2-azetidinone than for 2-oxetanone.