A theoretical study of the gas-phase pyrolysis of 2-azidoacetic acid

DFT and ah initio calculations up to the MP2 level have been performed to s tudy the pyrolysis of 2-azidoacetic acid (N3CH2COOH). Several molecular pro perties, such as conformational equilibrium, optimal geometry, ionization e nergies, and vibrational frequencies, have been computed for this acid. Oth er species involved in its pyrolysis were also fully optimized and correcte d for zero-point energies. In all cases, the calculated properties agree qu ite well with the observed experimental data. Two types of mechanisms were analyzed for the decomposition of N3CH2COOH. The first analyzed mechanism i s a multistep process analogous to the one traditionally proposed for alkyl azides. First, either the imine NHCHCOOH or the nitrene NCH2COOH is formed by the release of molecular N-2. Then, from these species, ejection of CO2 will produce methanimine (NHCH2), although other reaction channels may be expected. The second mechanism involves, after an initial distortion of the N3CH2COOH minimum geometry, a concerted dissociation step where N-2 and CO 2 are simultaneously ejected, yielding directly the imine NHCH2. Accordingl y to the present calculations, the second mechanism is the most favorable o ne, in clear agreement with recent experimental work.