Isomerizations of Isotopically Labeled Hydrocarbons

用氘标记的低分子量碳氢化合物将被合成并异构化，以确定异构化反应机理的详细细节。立体化学和动力学数据将用于评估这些异构化的过程。用氘标记手性反式-1,2-二乙基环丙烷研究环丙烷的单中心和双中心立体突变过程。丙烯、环丙烯、旋戊烷、乙烯基环丙烷和双环的异构化途径的立体化学研究ı3.1.1！庚-2-烯将与适当的氘标记和手性分子一起研究。同时，对乙烯基环丙烷热异构化成环戊烯的四种可能的立体化学途径进行了定量分析。这些分子足够小，高水平的分子轨道计算可以与实验结果结合使用，以便更好地理解这些过程。新的实验技术，振动圆二色性和可调谐二极管激光光谱学，将会对这些问题产生影响。这项来自有机动力学项目的拨款支持了雪城大学鲍德温教授的持续研究。这项研究将研究仅含碳、氢和氘的小分子中原子的重组（异构化）的细节。这些研究的结果可以与高水平的理论计算进行比较，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.