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Isomerizations of Isotopically Labeled Hydrocarbons

同位素标记的烃的异构化

基本信息

批准号：
0211120
负责人：
John Baldwin
金额：
$ 45万
依托单位：
Syracuse University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2002
资助国家：
美国
起止时间：
2002-07-15 至 2006-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=0211120&HistoricalAwards=false
关键词：
Isomerizations Isotopically Labeled Hydrocarbons

项目摘要

With the support of the Organic and Macromolecular Chemistry Program, Professor John E. Baldwin, of the Department of Chemistry at Syracuse University, is studying isomerization reactions of isotopically labeled hydrocarbons. Professor Baldwin is establishing the relative importance of one-center and two-center epimerizations in spiropentanes and cyclopropanes and obtaining the first experimental measures of secondary deuterium kinetic isotope effects on these stereomutations. In addition, he is exploring a number of other fundamental hydrocarbon isomerizations, including the conversion of cyclopropane to propylene via 1-propylidene, [1,3]-carbon shifts, [1,5]-hydrogen shifts, interconversion of bicyclo[5.1.0]octa-2,4-dienes via intermediate bicyclo[4.1.1]octa-2,4-dienes, and "carbo-Claisen" rearrangements.Thermal reactions of small hydrocarbon molecules play key roles both in fundamental organic reaction chemistry and in large-scale petrochemical processes such as hydrocarbon reforming. Professor John E. Baldwin, of the Department of Chemistry at Syracuse University, is studying the thermal transformations of a variety of small molecules. By incorporating stable isotopes, Professor Baldwin is able to obtain a comprehensive view of these transformations, obtaining insights into the reaction mechanisms which will ultimately lead to a fundamental understanding of how thermal reactions characteristic of simple organic chemicals occur.

在有机和高分子化学项目的支持下，约翰·E·锡拉丘兹大学化学系的鲍德温正在研究同位素标记的碳氢化合物的异构化反应。Baldwin教授正在建立螺戊烷和环丙烷中单中心和双中心差向异构化的相对重要性，并获得了第一个实验测量次级氘动力学同位素对这些立体突变的影响。此外，他正在探索许多其他基本的烃异构化，包括通过1-亚丙基、[1，3]-碳位移、[1，5]-氢位移将环丙烷转化为丙烯，通过中间体双环[4.1.1]辛-2，4-二烯将双环[5.1.0]辛-2，4-二烯相互转化，小烃分子的热反应在基础有机反应化学和大规模石油化学过程如烃重整中起关键作用。约翰·E.锡拉丘兹大学化学系的鲍德温正在研究各种小分子的热转化。通过结合稳定同位素，鲍德温教授能够全面了解这些转变，深入了解反应机制，最终从根本上了解简单有机化学品的热反应特征是如何发生的。