Theoretical insight into the mechanisms of the gas-phase decomposition of azidoacetone

A theoretical study of the mechanisms for the gas-phase decomposition of azidoacetone was performed using ab initio molecular orbital theory based on the QCISD(T)/aug-cc-pVTZ//MP2(full)/6-311++G(d,p) + 0.95 x ZPE method. The calculated results clearly show that the imine CH3C(O)N = CH2 formed through Curtius rearrangement route in conjunction with the cyclic amine and the imine CH3(CO)CH = NH play a crucial role in the gas-phase decomposition of azidoacetone. The fragmentation and/or isomerization these three intermediates giving rise to CH2CO, CH2 = NH, CO, CH3N = CH2, CH3CHO and HCN becomes the key reaction pathways. Our calculated results are in excellent consistent with the experimental findings.