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.

溶剂在确定课程时起着重要作用 和立体化学，以及化学和生化反应的速率。 因此，详细研究溶剂效应和 开发方法来预测其对给定过程的影响。 一个新 已经开发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 已经在一些系统上进行了测试，并发现结果 与实验测量一致。 该计划是为了进行实验和计算研究 在自然产品合成和 在生化研究中。 最初的大部分工作都会关注 使用许多跨越一定范围的反应对模型进行进一步测试 反应过程中极性特征的变化。 如果这些测试是 成功，可以预测应 可以观察到。 计划进一步开发模型，以包括效果 氢键，反应过程中腔大小的变化以及 动态溶质溶剂相互作用的变化。 结果的结果 调查应该可以更好地了解溶剂 与有机化合物相互作用。