Isotope Effects and Mechanisms in Eliminations and Other Proton Transfer Reactions

在有机动力学计划的支持下，教授 William H.小桑德斯罗切斯特大学的校长 研究了更换一个对化学行为的影响 一个分子中的一个或多个原子与一个同位素（一个原子与 相同性质的化学行为，但不同的原子 重量）。 这种反应速率的差异 更换将导致关于详细的结论 特定化学反应的途径（机制） 问题这些知识有助于反应的使用 合成工业和医药用化合物 兴趣 主要重点将放在探索的影响， 量子力学隧穿对原子核速率和同位素效应的影响 质子转移反应 为了获得这种 信息、同位素效应及其温度依赖性 将被确定为双分子消除， 脂肪族硝基化合物的去质子化。 另一 将探索的隧道的特点是 同位素效应的非累积行为 同位素效应（Isotopic Effect on Isotopic Effects） 动力学烯醇化物 形成和其他反应显示温度减弱 将研究依赖关系。 桑德斯医生会检测 假设这种异常温度依赖性可以 许多情况归因于通过一种以上碱的反应 物种 将进行同位素效应计算， 来解释实验结果。

With support from the Organic Dynamics Program, Professor William H. Saunders, Jr. of The University of Rochester will study the effect on chemical behavior caused by replacing one or more atoms in a molecule with an isotope (an atom with the same qualitative chemical behavior but a different atomic weight). The difference in reaction rates caused by such replacements will lead to conclusions about the detailed pathways (mechanisms) of the particular chemical reactions in question. Such knowledge facilitates the use of the reactions to synthesize compounds of industrial and pharmaceutical interest. Major emphasis will be placed on exploring the influence of quantum mechanical tunneling on rates and isotope effects in proton transfer reactions. In order to obtain such information, isotope effects and their temperature dependencies will be determined for bimolecular eliminations and deprotonation of aliphatic nitro compounds. Another characteristic of tunneling that will be explored is noncumulative behavior of isotope effects in multiply labeled species (isotope effects on isotope effects). Kinetic enolate formation and other reactions showing attenuated temperature dependencies will be studied. Dr. Saunders will test the hypothesis that such abnormal temperature dependence can in many instances be attributed to reaction via more than one base species. Isotope effect calculations will be performed as they are needed to interpret experimental results.