The Kinetics of Isomer-Specific Oxygen Exchange Reactions of Optically Active Alcohols

光学活性醇异构体特异性氧交换反应的动力学

• 批准号: 9007989
• 负责人: Margaret Merritt
• 金额: $ 12.72万
• 依托单位: Wellesley College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-07-01 至 1995-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9007989&HistoricalAwards=false
• 关键词: Kinetics; Isomer; Specific; Oxygen; Exchange

In this project ("The Kinetics of Isomer-Specific Oxygen Exchange Reactions of Optically Active Alcohols as a Function of Acid-Catalyzed Racemization") in the Organic Dynamics Program of the Chemistry Division, Professor Margaret V. Merritt of the Chemistry Department at Wellesley College will determine the rate constants for oxygen exchange for isomers as a function of racemization of a series of chiral alcohols. These detailed kinetic studies will enhance the understanding of reaction mechanisms and reaction intermediates in these and related systems. The rate constants for oxygen exchange as a function of racemization of a series of chiral alcohols will be used to probe the structural features that lead to asymmetric solvation of carbocation intermediates and to investigate the structure of water within the solvation sphere. The mechanistic conclusions will be based on the microscopic rate constants for three competing processes at the alpha carbon atom and the oxygen isotope effects for these processes. The three competing processes being studied are substitution (O-18 exchange) without inversion, substitution (O-18 exchange) with retention, and inversion without substitution.

在这个项目中（“异构体特异性氧的动力学 光学活性醇的交换反应 酸催化的外消旋反应”）在有机动力学中的应用 化学系的程序，教授玛格丽特V。 韦尔斯利学院化学系的梅里特将 确定异构体的氧交换速率常数 作为一系列手性醇的外消旋化的函数。 这些详细的动力学研究将增进对 反应机理和反应中间体， 相关系统。 氧交换的速率常数是以下的函数： 一系列手性醇的外消旋将被用来 探索导致不对称溶剂化的结构特征 的碳阳离子中间体，并研究其结构 溶剂化层中的水。 机械论 结论将基于微观速率常数， 三个竞争过程在α碳原子和 氧同位素对这些过程的影响。 三 正在研究的竞争过程是取代（O-18 交换）无转化，取代（O-18交换）有 保留和无取代的反转。