Isomerizations of Isotopically Labeled Hydrocarbons

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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.