15337-44-7Relevant articles and documents
Gas-Phase Reactions of (CH3)2N Radicals with NO and NO2
Lazarou, Yannis G.,Kambanis, Kyriakos G.,Papagiannakopoulos, Panos
, p. 2110 - 2115 (2007/10/02)
The absolute rate constants for the reactions of (CH3)2N radicals with NO and NO2 were determined in the gas phase and at room temperature by using the very low pressure reactor (VLPR) technique.The rates were k(CH3)2N + NO = (8.53 +/- 1.42) x 1E-14 Cm3 molecule-1s-1 and k(CH3)2N + NO2 = (9.08 +/- 1.36) x 1E-13 cm3 molecule-1s-1.The reaction with NO2 proceeds via two competitive pathways: the recombination patway (CH3)2N + NO2 -> (CH3)2NNO2, with a rate constant k2a = (3.18 +/- 0.48) x 1E-13 cm3molecule-1s-1, and the oxidation patway (CH3)2N + NO2 -> (CH3)2NONO* -> (CH3)2NO + NO, with a rate constant k2b = (6.36 +/- 0.74) x 1E-13 cm3molecule-1s-1.The oxidation pathway is ca. 2.2 times faster than the recombination one, and the ratio k2a/k2b = 0.45 +/- 0.15.Conventional transition state theory analysis indicates that the involved transition states are loose, with the NN or bond lengths equal to ca. 2.5 Angstroem.
Hydrogen Abstraction from Amines: Formation of Aminyl vs. α-Aminoalkyl Radicals
Nazran, A. S.,Griller, D.
, p. 1970 - 1971 (2007/10/02)
A series of electron paramagnetic experiments were carried out which showed that dialkylaminyl radicals do not readily attack dialkylamines to form α-aminoalkyl radicals.These results disprove earlier conclusions that such processes were the major pathways for formation of α-aminoalkyl radicals in free radical reactions involving dialkylamines.By contrast, tert-butoxyl radicals were found to efficiently abstract hydrogen from amines.Rate constants for C-H and N-H abstraction by tert-butoxyl were respectively 6.5 x 107 and 1.1 x 107 for Me2NH, 6.6 x 107 and 1.0 x 107 for Et2NH, 1.3 x 107 and 3 x 106 for n-PrNH2, 7 x 106 and 3 x 106 for n-BuNH2, and 3.3 x 106 for t-BuNH2 (units M-1 s-1).
