The rate of oxidation of tertiary amines by aqueous hydrogen peroxide is increased in the presence of acetonitrile due to the formation of a reactive intermediate. The active oxidant, presumably peroxyacetimidic acid, was quantified by a photometric method. Activation parameters of the acetonitrile-assisted and non-assisted oxidations are given in the temperature range 20 to 40 °C. The increased rate of the assisted oxidation is explained by the low enthalpy of activation although the entropy of activation is more negative due to a highly ordered transition state.
过氧化氢水溶液氧化叔胺的速率在有
乙腈存在的情况下会增加,这是由于形成了一种活性中间体。活性氧化剂(可能是过氧乙酰亚
氨酸)用光度法进行了定量。给出了
乙腈辅助氧化和非辅助氧化在 20 至 40 °C 温度范围内的活化参数。虽然由于过渡态高度有序,活化熵为负值,但活化焓较低,这解释了辅助氧化速率增加的原因。