440085-31-4Relevant academic research and scientific papers
Notable substituent effects on the rate constant of thermal denitrogenation of cyclic azoalkanes: Strong evidence for a stepwise denitrogenation mechanism
Ishihara, Chizuko,Abe, Manabu
scheme or table, p. 1615 - 1618 (2011/09/20)
The thermal denitrogenation rates (k) of a series of 7,7-dimethoxy-1,4- diaryl-2,3-diazabicyclo[2.2.1]hept-2-ene derivatives 2 with a variety of aryl groups (p-CNC6H4, C6H5, p-MeC 6H4, p-MeOC6H4) were determined to investigate the denitrogenation mechanism. A linear correlation (r = 0.988) between the relative rate-constant (log krel) of the denitrogenation reaction and Arnold's σ α parameter for benzylic-type radical-stabilization was observed. However, the relative rate-constant was not correlated with the substituent effect on the lifetime of the resulting singlet diradicals DR2. These results indicate that the rate-determining step of denitrogenation of 7,7-dimethoxy-2,3-diazabicyclo[2.2. 1]hept-2-ene derivatives involves stepwise C-N bond cleavage. CSIRO 2010.
