Isomerizations of Isotopically Labeled Hydrocarbons

在有机化学和高分子化学项目的支持下，锡拉丘兹大学化学系的约翰·E·鲍德温教授正在研究同位素标记的碳氢化合物的异构化反应。鲍德温教授正在确定螺戊烷和环丙烷中单中心和双中心异构化的相对重要性，并首次获得了次级氚动力学同位素对这些立体变异的影响的实验测量方法。此外，他还在探索其他一些基本的烃类异构化反应，包括通过1-亚丙烯将环丙烷转化为丙烯，[1，3]-碳转移，[1，5]-氢转移，通过中间双环[4.1.1]八-2，4-二烯和“碳克莱森”重排将双环[5.1.0]八-2，4-二烯相互转化。碳氢化合物小分子的热反应在基础有机反应化学和大规模石化过程中都发挥着关键作用，如烃类重整。锡拉丘兹大学化学系的约翰·E·鲍德温教授正在研究各种小分子的热转变。通过引入稳定的同位素，鲍德温教授能够对这些转变有一个全面的看法，对反应机理有深入的了解，这最终将导致对简单有机化学品的热反应如何发生的基本了解。

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.