Carbanions and Physical Organic Chemistry

将采用实验和计算方法来确定 各种碳氢化合物的动力学酸度实验 方法将包括确定汇率， 铯和锂催化的环己胺-N-叔 通过氚NMR测定环己基酰胺。将确定一些费率， 用环己胺-N-d2进行氘交换， 光谱和氘NMR。理论计算将 进行质子转移反应， 碳氢化合物和碱，并与实验结果进行比较。 离子对SN 2置换反应的计算将是 持续期间内的这些反应表现出不寻常的高度弯曲转变 状态，并可能给出不同于 相应的离子反应。 %%% 有机动力学计划的这笔赠款支持 安德鲁·斯特雷特维泽教授在大学的持续工作 来自加州伯克利。极弱酸性的酸度 碳氢化合物将由最近开发的敏感 技术.这将扩大一个重要的知识体系。 理论计算将涉及的酸度， 碳氢化合物，并将结果与实验结果进行比较 调查结果。这项工作将提供一个基本的理解， 弱酸性碳氢化合物及其对化学品的影响 碳氢化合物中碳氢键的反应性。额外 将对基本位移进行计算 有机化学中的反应过程。初步核算 在这个反应过程中显示了一种不寻常的几何形状， 这项工作将继续进行。

Experimental and computational methods will be applied to determine the kinetic acidities of a variety of hydrocarbons. Experimental methods will include the determination of exchange rates from cyclohexylamine-N-t catalyzed by cesium and lithium cyclohexylamides by tritium NMR. Some rates will be determined for deuterium exchange with cyclohexylamine-N-d2 using mass spectroscopy and deuterium NMR. Theoretical calculations will be carried out for proton transfer reaction between various hydrocarbons and bases, and compared to experimental results. Calculations of ion-pair SN2 displacement reactions will be continued. These reactions show unusual highly bent transition states and may give relative reactivities different from the corresponding ionic reactions. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Andrew Streitwieser at the University of California, Berkeley. The acidity of very weakly acidic hydrocarbons will be determined by recently developed sensitive techniques. This will extend an important body of knowledge. Theoretical calculations will be made that relate to the acidity of hydrocarbons and the results will be compared to the experimental findings. This work will provide a fundamental understanding of weakly acidic hydrocarbons and the consequences to chemical reactivity of the carbon-hydrogen bond in hydrocarbons. Additional calculations will be carried out on a fundamental displacement reaction process in organic chemistry. Preliminary calculations have shown an unusual geometry in the course of this reaction and this work will be continued.