Isomerizations of Isotopically Labeled Hydrocarbons

用氘标记的低分子量碳氢化合物将被 合成和异构化，以确定亲密 异构化反应机理的细节。 立体化学和动力学数据将用于评估过程 这些异构化。单中心和双中心立体突变 用氘标记的方法研究了环丙烷的反应过程 手性反式-1，2-二乙炔基环丙烷。的立体化学 丙二烯，环丙烯，螺戊烷， 乙烯基环丙烷和双环[3.1.1！庚-2-烯将被研究 用适当的氘标记和手性分子。 此外，四种可能的立体化学途径可用于 乙烯基环丙烷到环戊烯的热异构化将是 量化。这些分子足够小， 水平分子轨道计算可以结合 为了更好地理解这些实验结果， 流程.新的实验技术，振动圆 二向色性和可调谐二极管激光光谱，将带来 承担这些问题。 有机动力学计划的这笔赠款支持 鲍德温教授继续研究， 锡拉丘兹。这项研究将研究的细节， 小分子中原子的重组（异构化）， 只含有碳氢和氘的结果予以 研究可以与高级理论计算相比较， 以便进一步了解这些反应。

Low molecular weight hydrocarbons, labeled with deuterium, will be synthesized and isomerized in order to determine the intimate details of the mechanisms of the isomerization reactions. Stereochemical and kinetic data will be used to assess the course of these isomerizations. One- and two-centered stereomutation processes of cyclopropane will be studied with deuterium labeled chiral trans-1,2-diethynylcyclopropane. The stereochemistry of the isomerization pathways of allene, cyclopropene, spiropentane, vinylcyclopropane, and bicyclo ı3.1.1! hept-2-ene will be studied with the appropriately deuterium labeled and chiral molecules. Also, the four possible stereochemical pathways available for the vinylcyclopropane to cyclopentene thermal isomerization will be quantified. These molecules are sufficiently small that high level molecular orbital calculations can be used in conjunction with the experimental results for a better understanding of these processes. New experimental techniques, vibrational circular dichroism and tunable diode laser spectroscopy, will be brought to bear on these problems. This grant from the Organic Dynamics Program supports the continuing research of Professor Baldwin at the University of Syracuse. This research will study the details of the reorganization (isomerization) of atoms in small molecules that contain only carbon, hydrogen, and deuterium. The results of these studies can be compared to high level theoretical calculations in order to gain further insight about these reactions.