T-for-H交換反応におけるシクロアミンの反応性の速度論的解析

抄録

The hydrogen-isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly (vinyl alcohol) and each cycloamine dissolved in 1, 4-dioxane has been observed at 50-90°C. Consequently, the quantitative relation was obtained between the reaction time and the increase in the tritium activity of the cycloamine. The reaction was dynamically analyzed with both the A''-McKay plot method and data observed. Moreover, in order to clarify the effect of the relative atomic charge of the N atom (in the amino group) on the reactivity of the cycloamine, the MOPAC method was introduced. As to cycloamine, the following three matters have been consequently found in the T-for-H exchange reaction: (1) the reactivity of each cycloamine decreases with increasing the number of carbon atoms in the ring of cycloamine, (2) the rate constant (k) for each cycloamine depends on the reaction temperature, (3) the correlation is found between the relative atomic charge of the N atom in the NH₂ group and k for the cycloamine.