Radical pathways in the thermal decomposition of pyridine and diazines: a laser pyrolysis and semi-empirical study

The mechanisms of thermal decomposition of pyridine and the three isomeric diazines have been investigated by IR laser pyrolysis in conjunction with stable end-product analysis by FTIR, NMR and GC-MS, and radical detection by EPR spectroscopy, Calculations at semi-empirical and ab initio levels have provided confirmation of potential reaction pathways, For pyridine, reaction is initiated by formation of pyridyl radicals, as indicated by extensive isotope exchange with added deuterium, Experiments with bromopyridines show that open chain radicals arising from ring opening of 2-pyridyl and 3-pyridyl radicals each lead to stable gaseous produces, while 4-pyridyl radicals produce solid deposits, and may be the principal agents in soot formation, The evidence suggests that 1,2-diazine decomposes via a molecular route leading to stoichiometric production of HCN and C2H2, while 1,3- and 1,4-diazine follow a pattern of H loss and ring radical opening analogous to that of pyridine.