SOLVENT EFFECTS ON RATES OF ORGANIC REACTIONS

溶剂对有机反应速率的影响

• 批准号: 2900862
• 负责人: KENNETH B WIBERG
• 金额: $ 14.85万
• 依托单位: YALE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-04-01 至 2001-09-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2900862
• 关键词: chemical kinetics; chemical models; chemical reaction; computer simulation; hydrogen bond; intermolecular interaction; molecular polarity; organic chemicals; solvents

Solvents play a major role in determining the course, the regiochemistry and stereochemistry,a nd the rates of chemical and biochemical reactions. Therefore it is of importance to study solvent effects in detail, and to develop methods for predicting their effect on a given process. A new solvent effect model has been developed that is based on ab initio molecular orbital theory, and does not employ any empirical parameters. It has been tested on a few systems, and was found to give results in agreement with experimental measurements. The plan is to carry out both experimental and computational studies of effects in systems that are of importance in natural product synthesis and in biochemical studies. Much of the initial work will be concerned with further tests of the model using a number of reactions that span a range of changes in polar character during the reaction. If these tests are successful, it will be possible to make predictions of effects that should be observed. Further development of the model is planned in order to include the effects of hydrogen bonding, changes in cavity size during the reaction, and changes in dynamical solute-solvent interactions. The results of this investigation should allow a much better understanding of how solvents interact with organic compounds.

溶剂在决定区域化学过程中起着主要作用。 和立体化学，以及化学反应和生化反应的速度。 因此，对溶剂效应进行详细的研究具有重要的意义。 开发预测它们对给定过程的影响的方法。一种新的 建立了基于从头算的溶剂效应模型。 分子轨道理论，不使用任何经验参数。它 已经在几个系统上进行了测试，并在 与实验测量结果一致。 该计划将进行实验和计算研究，以 在天然产物合成和合成中具有重要作用的体系中的影响 在生化研究中。许多最初的工作将涉及到 使用一系列反应对模型进行进一步测试，这些反应跨越了 反应过程中极性的变化。如果这些测试是 成功的话，就有可能预测出应该 被人观察。 计划进一步开发该模型，以便将这些影响包括在内 氢键，反应过程中空腔大小的变化，以及 动态溶质-溶剂相互作用的变化。这样做的结果 调查应该让我们更好地了解溶剂是如何 与有机化合物相互作用。