溶剂对甲基转移反应的影响. 2. 2. 2. 这是一个很棒的节目. 胺基与三甲基硫盐的反应
H Castejon1, K B Wiberg, S Sklenak
1Science Computing, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Journal of the American Chemical Society
|June 21, 2001
概括
研究氨和与三甲基硫离子的反应,揭示了溶剂效应. 增加溶剂极性增强了激活自由能量,改变了反应外热度,与实验数据保持一致.
科学领域:
- 计算化学是一种计算化学.
- 物理有机化学 有机化学
背景情况:
- 三甲基硫离子与核友的反应性在有机合成中至关重要.
- 了解溶剂对反应机制的影响是控制化学转换的关键.
研究的目的:
- 为了研究氨和皮里丁与三甲基硫离子的气相和溶液相反应机制.
- 阐明溶剂极性对反应路径,过渡状态和能量学的影响.
主要方法:
- 密度函数理论 (DFT) 对气相反应的B3LYP/6-31+G水平的计算.
- 自相一致的同位密度极化连续模型 (SCI-PCM) 对于环素和二甲基硫氧化物 (DMSO) 溶剂效应.
- 蒙特卡洛自由能量扰动方法用于水溶剂效应.
主要成果:
- 气相反应表现出复杂的路径,具有多个中间体和一个复杂的过渡状态.
- 环素保留了气相通路的能量变化;DMSO通过消除物种来简化了配置文件.
- 激活的自由能量随着溶剂极性而增加,对于氨和的反应.
结论:
- 溶剂极性显著影响三甲基硫离子与氨和的反应机制和能量.
- 在激活自由能量和外热度中观察到的趋势在不同的溶剂和计算方法中一致.
- 计算结果与实验观察表明,溶剂对反应速率的影响与实验观察有很好的一致性.
相关概念视频
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