SOLVENT EFFECTS ON RATES OF ORGANIC REACTIONS

溶剂对有机反应速率的影响

• 批准号: 2685087
• 负责人: KENNETH B WIBERG
• 金额: $ 14.51万
• 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 2000-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2685087
• 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.

溶剂在决定过程中起主要作用，区域化学 和立体化学，以及化学和生物化学反应的速率。 因此，详细研究溶剂效应， 开发预测它们对给定过程的影响的方法。 一个新 溶剂效应模型是建立在从头算基础上的 分子轨道理论，并且不采用任何经验参数。 它 已经在几个系统上进行了测试，并发现在 与实验测量结果一致。 该计划是进行实验和计算研究， 在天然产物合成中具有重要意义的系统中的作用， 在生物化学研究中。 大部分的初步工作将涉及 使用跨越一系列反应的模型的进一步测试 反应过程中极性的变化。 如果这些测试 如果成功，就有可能预测出 被观察。 计划进一步开发该模型，以包括 氢键，反应过程中空腔尺寸的变化，以及 动态溶质-溶剂相互作用的变化。 的结果 研究应该使我们更好地了解溶剂 与有机化合物相互作用。