beta-lactam is formed immediately after the laser pulse but gamma-lactam is formed from both slow and fast processes. It is concluded that beta-lactam is formed from the diazoamide excited state via the rearrangement in the excited state (RIES) mechanism and that gamma-lactam is formed from both RIES and carbene. In methanol, both carbene decay and the rise of amide ether product are observed directly. Predictions
超
快红外光谱表明,在
氯仿中,β-内酰胺在激光脉冲后立即形成,而 γ-内酰胺则由慢速和快速过程形成。得出的结论是,β-内酰胺是通过激发态重排 (RIES) 机制从重氮酰胺激发态形成的,γ-内酰胺是由 RIES 和卡宾形成的。在
甲醇中,直接观察到卡宾衰变和酰胺醚产物的上升。密度泛函理论计算的预测与这些观察结果一致。