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Pericyclic Transition Structures

周环过渡结构

基本信息

批准号：
8919768
负责人：
Henry Shine
金额：
$ 27.99万
依托单位：
Texas Tech University
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：
1990-02-01 至 1994-01-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=8919768&HistoricalAwards=false
关键词：
Pericyclic Transition Structures

项目摘要

In this project in the Organic Dynamics Program, Professor Henry J. Shine will study "Pericyclic Transition Structures" in the Chemistry Department at Texas Tech University. Professor Shine is collaborating with Professor William H. Saunders in the Chemistry Department at the University of Rochester. In this study heavy atom kinetic isotope effects with specifically labelled substrates are being measured and bond order modeling calculations are being carried out in order to define the transition structures of reactions that are known to be pericyclic. Heavy atom (carbon, nitrogen, and, oxygen) kinetic isotope effects (KIE) and bond order modeling calculations are being made in order to define the transition structures of several pericyclic reactions. Reactions being studied are the aromatic Claisen rearrangement (allyl phenyl ether), the benzidine rearrangement (hydrazobenzene), and the aliphatic Claisen rearrangement (allyl vinyl ether and two of its derivatives). The objective in the aromatic Claisen rearrangement and in the benzidine rearrangement is to use them to probe along the reaction coordinate for coupled motion of carbon atoms not directly involved in bond breaking and making. In the aliphatic Claisen rearrangements the objective is to define their transition structures and synchronicities, over which controversy has arisen from theoretical treatments. Modeling calculations will be made to fit KIE to bond orders and, hence, to optimized transition structures.

在这个有机动力学项目中，亨利J. Shine将研究"周环过渡结构"，德州理工大学化学系教授 Shine与William H.桑德斯在罗切斯特大学化学系。在本文研究了重原子动力学同位素效应，标记的基板正在测量和键级建模正在进行计算，以确定已知的反应的过渡结构周环的重原子（碳、氮和氧）动力学同位素影响（KIE）和键级建模计算正在进行为了确定几个过渡结构，周环反应正在研究的反应是芳族克莱森重排（烯丙基苯基醚），联苯胺重排（氢化偶氮苯）和脂族 Claisen重排反应（烯丙基乙烯基醚及其两种衍生物）。在芳香克莱森的目标重排和联苯胺重排是使用它们沿沿着反力坐标探测耦合运动不直接参与键的断裂和形成的碳原子。在脂肪族克莱森重排中，目标是定义它们的过渡结构和同步性，这一争议源于理论治疗。将进行建模计算，以使KIE适合债券订单并因此涉及优化的过渡结构。